The Role of Specific Ion Effects in Ion Transport: The Case of Nitrate and Thiocyanate

Lovering, Kaitlin; Nayak, Srikanth; Bu, Wei; Uysal, Ahmet

doi:10.1021/acs.jpcc.9b09288

Title: The Role of Specific Ion Effects in Ion Transport: The Case of Nitrate and Thiocyanate

Journal Article · 04 December 2019 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.9b09288 · OSTI ID:1606542

Lovering, Kaitlin ^[1]; Nayak, Srikanth ^[1]; Bu, Wei ^[2];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Chicago, IL (United States). NSF’s ChemMatCARS

The selective transport of trivalent rare earth metals from aqueous to organic environments with the help of amphiphilic "extractants" is an industrially important process. When the amphiphilic extractant is positively charged or neutral, the coextracted background anions are not only necessary for charge balance but also have a large impact on extraction efficiency and selectivity. In particular, the opposite selectivity trends observed throughout the lanthanide series in the presence of nitrate and thiocyanate ions have not been explained. To understand the role of background anions in the phase transfer of lanthanide cations, in this work we use a positively charged long-chain aliphatic molecule, modeling a common extractant, and gain molecular level insight into interfacial headgroup-anion interactions. By combining surface sensitive sum frequency generation spectroscopy with X-ray reflectivity and grazing incidence X-ray diffraction, we observed qualitative differences in the orientational and overall interfacial structure of nitrate and thiocyanate solutions at a positively charged Langmuir monolayer. Though nitrate adsorbs without dramatic changes to the solvation structure at the interface or the monolayer ordering, thiocyanate significantly alters the water structure and reduces monolayer ordering. We suggest that these qualitatively different adsorption trends help explain a reversal in system selectivity toward lighter or heavier lanthanides in solvent extraction systems in the presence of nitrate or thiocyanate anions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1606542

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 1 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

Molecular Structure and Dynamics of Water at the Water-Air Interface Studied with Surface-Specific Vibrational Spectroscopy Bonn, Mischa; Nagata, Yuki; Backus, Ellen H. G. Angewandte Chemie International Edition, Vol. 54, Issue 19 https://doi.org/10.1002/anie.201411188	journal	April 2015
Solvent Extraction: Structure of the Liquid-Liquid Interface Containing a Diamide Ligand Scoppola, Ernesto; Watkins, Erik B.; Campbell, Richard A. Angewandte Chemie International Edition, Vol. 55, Issue 32 https://doi.org/10.1002/anie.201603395	journal	June 2016
Theory and Applications of Sum-Frequency Generations Lin, C. K.; Yang, L.; Hayashi, M. Journal of the Chinese Chemical Society, Vol. 61, Issue 1 https://doi.org/10.1002/jccs.201300416	journal	October 2013
Zur Lehre von der Wirkung der Salze: Zweite Mittheilung Hofmeister, Franz Archiv für Experimentelle Pathologie und Pharmakologie, Vol. 24, Issue 4-5 https://doi.org/10.1007/BF01918191	journal	February 1888
A simple empirical model describing the thermodynamics of hydration of ions of widely varying charges, sizes, and shapes Marcus, Yizhak Biophysical Chemistry, Vol. 51, Issue 2-3 https://doi.org/10.1016/0301-4622(94)00051-4	journal	August 1994
Liquid Surface X-Ray Scattering Bera, Mrinal K.; Bu, Wei; Uysal, Ahmet Physical Chemistry of Gas-Liquid Interfaces https://doi.org/10.1016/B978-0-12-813641-6.00007-8	book	June 2018
Investigations of the Hofmeister series and other specific ion effects using lipid model systems Leontidis, Epameinondas Advances in Colloid and Interface Science, Vol. 243 https://doi.org/10.1016/j.cis.2017.04.001	journal	May 2017
Effect of long-range interactions on ion equilibria in liquid–liquid extraction Dufrêche, J. -F.; Zemb, Th. Chemical Physics Letters, Vol. 622 https://doi.org/10.1016/j.cplett.2014.11.028	journal	February 2015
The nature of salt effect in enhancing the extraction of rare earths by non-functional ionic liquids: Synergism of salt anion complexation and Hofmeister bias Sun, Pan; Huang, Kun; Liu, Huizhou Journal of Colloid and Interface Science, Vol. 539 https://doi.org/10.1016/j.jcis.2018.12.058	journal	March 2019
Model for Metal Extraction from Chloride Media with Basic Extractants: A Coordination Chemistry Approach Lommelen, Rayco; Vander Hoogerstraete, Tom; Onghena, Bieke Inorganic Chemistry, Vol. 58, Issue 18 https://doi.org/10.1021/acs.inorgchem.9b01782	journal	August 2019
New Information on the Ion-Identity-Dependent Structure of Stern Layer Revealed by Sum Frequency Generation Vibrational Spectroscopy Lovering, Kaitlin A.; Bertram, Allan K.; Chou, Keng C. The Journal of Physical Chemistry C, Vol. 120, Issue 32 https://doi.org/10.1021/acs.jpcc.6b05564	journal	August 2016
Conformational Changes of Methacrylate-Based Monomers at the Air–Liquid Interface Due to Bulky Substituents Premadasa, Uvinduni I.; Adhikari, Narendra M.; Baral, Susil The Journal of Physical Chemistry C, Vol. 121, Issue 31 https://doi.org/10.1021/acs.jpcc.7b05433	journal	July 2017
Two-Step Adsorption of PtCl ₆ ^2– Complexes at a Charged Langmuir Monolayer: Role of Hydration and Ion Correlations Uysal, Ahmet; Rock, William; Qiao, Baofu The Journal of Physical Chemistry C, Vol. 121, Issue 45 https://doi.org/10.1021/acs.jpcc.7b09350	journal	November 2017
Electrolyte and Temperature Effects on Third-Order Susceptibility in Sum-Frequency Generation Spectroscopy of Aqueous Salt Solutions Joutsuka, Tatsuya; Morita, Akihiro The Journal of Physical Chemistry C, Vol. 122, Issue 21 https://doi.org/10.1021/acs.jpcc.8b02445	journal	May 2018
Solvent Isotopic Effects on a Surfactant Headgroup at the Air–Liquid Interface Premadasa, Uvinduni I.; Moradighadi, Negar; Kotturi, Kondalarao The Journal of Physical Chemistry C, Vol. 122, Issue 28 https://doi.org/10.1021/acs.jpcc.8b03680	journal	June 2018
Heavy Anionic Complex Creates a Unique Water Structure at a Soft Charged Interface Rock, William; Qiao, Baofu; Zhou, Tiecheng The Journal of Physical Chemistry C, Vol. 122, Issue 51 https://doi.org/10.1021/acs.jpcc.8b08419	journal	November 2018
Quantifying Double-Layer Potentials at Liquid–Gas Interfaces from Vibrational Sum-Frequency Generation García Rey, Natalia; Weißenborn, Eric; Schulze-Zachau, Felix The Journal of Physical Chemistry C, Vol. 123, Issue 2 https://doi.org/10.1021/acs.jpcc.8b10097	journal	December 2018
Specific Ion Effects at the Interface of Nanometer-Sized Droplets in Water: Structure and Stability Zdrali, E.; Okur, H. I.; Roke, S. The Journal of Physical Chemistry C, Vol. 123, Issue 27 https://doi.org/10.1021/acs.jpcc.9b01001	journal	June 2019
pH-Dependent Inversion of Hofmeister Trends in the Water Structure of the Electrical Double Layer DeWalt-Kerian, Emma L.; Kim, Sun; Azam, Md. Shafiul The Journal of Physical Chemistry Letters, Vol. 8, Issue 13 https://doi.org/10.1021/acs.jpclett.7b01005	journal	June 2017
Salt Promotes Protonation of Amine Groups at Air/Water Interface Sung, Woongmo; Avazbaeva, Zaure; Kim, Doseok The Journal of Physical Chemistry Letters, Vol. 8, Issue 15 https://doi.org/10.1021/acs.jpclett.7b01198	journal	July 2017
2D H-Bond Network as the Topmost Skin to the Air–Water Interface Pezzotti, Simone; Galimberti, Daria Ruth; Gaigeot, Marie-Pierre The Journal of Physical Chemistry Letters, Vol. 8, Issue 13 https://doi.org/10.1021/acs.jpclett.7b01257	journal	June 2017
The Topmost Water Structure at a Charged Silica/Aqueous Interface Revealed by Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy Urashima, Shu-hei; Myalitsin, Anton; Nihonyanagi, Satoshi The Journal of Physical Chemistry Letters, Vol. 9, Issue 14 https://doi.org/10.1021/acs.jpclett.8b01650	journal	June 2018
Specific Ion Effects on Particle Aggregation Induced by Monovalent Salts within the Hofmeister Series Oncsik, Tamas; Trefalt, Gregor; Borkovec, Michal Langmuir, Vol. 31, Issue 13 https://doi.org/10.1021/acs.langmuir.5b00225	journal	March 2015
Observation of Ordered Structures in Counterion Layers near Wet Charged Surfaces: A Potential Mechanism for Charge Inversion Miller, Mitchell; Chu, Miaoqi; Lin, Binhua Langmuir, Vol. 32, Issue 1 https://doi.org/10.1021/acs.langmuir.5b04058	journal	December 2015
Atomic Number Dependent “Structural Transitions” in Ordered Lanthanide Monolayers: Role of the Hydration Shell Miller, Mitchell; Chu, Miaoqi; Lin, Binhua Langmuir, Vol. 33, Issue 6 https://doi.org/10.1021/acs.langmuir.6b04609	journal	January 2017
Specific Salt Effect on the Interaction between Rare Earth Ions and Trioctylphosphine Oxide Molecules at the Organic–Aqueous Two-Phase Interface: Experiments and Molecular Dynamics Simulations Sun, Pan; Huang, Kun; Liu, Huizhou Langmuir, Vol. 34, Issue 38 https://doi.org/10.1021/acs.langmuir.8b02301	journal	April 2018
Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides Baldwin, Anna G.; Ivanov, Alexander S.; Williams, Neil J. ACS Central Science, Vol. 4, Issue 6 https://doi.org/10.1021/acscentsci.8b00223	journal	June 2018
Vibrational Sum Frequency Spectroscopy Studies of the Influence of Solutes and Phospholipids at Vapor/Water Interfaces Relevant to Biological and Environmental Systems Johnson, C. Magnus; Baldelli, Steven Chemical Reviews, Vol. 114, Issue 17 https://doi.org/10.1021/cr4004902	journal	January 2014
Biological Macromolecules at Interfaces Probed by Chiral Vibrational Sum Frequency Generation Spectroscopy Yan, Elsa C. Y.; Fu, Li; Wang, Zhuguang Chemical Reviews, Vol. 114, Issue 17 https://doi.org/10.1021/cr4006044	journal	January 2014
Counterion Effect on Interfacial Water at Charged Interfaces and Its Relevance to the Hofmeister Series Nihonyanagi, Satoshi; Yamaguchi, Shoichi; Tahara, Tahei Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja412952y	journal	April 2014
Enhanced Anion Exchange for Selective Sulfate Extraction: Overcoming the Hofmeister Bias Fowler, Christopher J.; Haverlock, Tamara J.; Moyer, Bruce A. Journal of the American Chemical Society, Vol. 130, Issue 44 https://doi.org/10.1021/ja806511b	journal	November 2008
Oriented Thiocyanate Anions at the Air−Electrolyte Interface and Its Implications on Interfacial Water - A Vibrational Sum Frequency Spectroscopy Study Viswanath, P.; Motschmann, H. The Journal of Physical Chemistry C, Vol. 111, Issue 12 https://doi.org/10.1021/jp0702649	journal	March 2007
Kinetics of Triton-X100 Transfer Across the Water/Dodecane Interface: Analysis of the Interfacial Tension Variation Gassin, Pierre-Marie; Martin-Gassin, Gaelle; Meyer, Daniel The Journal of Physical Chemistry C, Vol. 116, Issue 24 https://doi.org/10.1021/jp302514k	journal	June 2012
Direct and Reverse Hofmeister Effects on Interfacial Water Structure Flores, Sarah C.; Kherb, Jaibir; Cremer, Paul S. The Journal of Physical Chemistry C, Vol. 116, Issue 27 https://doi.org/10.1021/jp3029352	journal	June 2012
Basic Theory of Surface Sum-Frequency Generation Shen, Y. R. The Journal of Physical Chemistry C, Vol. 116, Issue 29 https://doi.org/10.1021/jp305539v	journal	July 2012
X-ray Reflectivity Reveals a Nonmonotonic Ion-Density Profile Perpendicular to the Surface of ErCl ₃ Aqueous Solutions Luo, Guangming; Bu, Wei; Mihaylov, Miroslav The Journal of Physical Chemistry C, Vol. 117, Issue 37 https://doi.org/10.1021/jp4067247	journal	September 2013
Observation of a Rare Earth Ion–Extractant Complex Arrested at the Oil–Water Interface During Solvent Extraction Bu, Wei; Yu, Hao; Luo, Guangming The Journal of Physical Chemistry B, Vol. 118, Issue 36 https://doi.org/10.1021/jp505661e	journal	August 2014
X-ray Studies of Interfacial Strontium–Extractant Complexes in a Model Solvent Extraction System Bu, Wei; Mihaylov, Miroslav; Amoanu, Daniel The Journal of Physical Chemistry B, Vol. 118, Issue 43 https://doi.org/10.1021/jp508430e	journal	October 2014
Specificity and Variation of Length Scale over Which Monovalent Halide Ions Neutralize a Charged Interface Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan The Journal of Physical Chemistry C, Vol. 119, Issue 13 https://doi.org/10.1021/jp512233g	journal	March 2015
Variation of Ionic Strength Reveals the Interfacial Water Structure at a Charged Mineral Surface Jena, Kailash C.; Hore, Dennis K. The Journal of Physical Chemistry C, Vol. 113, Issue 34 https://doi.org/10.1021/jp905475m	journal	July 2009
Vibrational Sum Frequency Generation Spectroscopic Investigation of the Interaction of Thiocyanate Ions with Zwitterionic Phospholipid Monolayers at the Air−Water Interface Viswanath, P.; Aroti, A.; Motschmann, H. The Journal of Physical Chemistry B, Vol. 113, Issue 44 https://doi.org/10.1021/jp906455k	journal	November 2009
The Effect of Salt on the Water Structure at a Charged Solid Surface: Differentiating Second- and Third-order Nonlinear Contributions Jena, Kailash C.; Covert, Paul A.; Hore, Dennis K. The Journal of Physical Chemistry Letters, Vol. 2, Issue 9 https://doi.org/10.1021/jz200251h	journal	April 2011
Electric Field Reversal of Na ₂ SO ₄ , (NH ₄ ) ₂ SO ₄ , and Na ₂ CO ₃ Relative to CaCl ₂ and NaCl at the Air/Aqueous Interface Revealed by Heterodyne Detected Phase-Sensitive Sum Frequency Hua, Wei; Jubb, Aaron M.; Allen, Heather C. The Journal of Physical Chemistry Letters, Vol. 2, Issue 20 https://doi.org/10.1021/jz200888t	journal	September 2011
Specific Anion Effects on Water Structure Adjacent to Protein Monolayers ^† Chen, Xin; Flores, Sarah C.; Lim, Soon-Mi Langmuir, Vol. 26, Issue 21 https://doi.org/10.1021/la1015862	journal	November 2010
Sum-Frequency Spectroscopic Study of Langmuir Monolayers of Lipids Having Oppositely Charged Headgroups Sung, Woongmo; Seok, Sangjun; Kim, Doseok Langmuir, Vol. 26, Issue 23 https://doi.org/10.1021/la103129z	journal	December 2010
Surface properties probed by second-harmonic and sum-frequency generation Shen, Y. R. Nature, Vol. 337, Issue 6207 https://doi.org/10.1038/337519a0	journal	February 1989
Beyond Hofmeister Jungwirth, Pavel; Cremer, Paul S. Nature Chemistry, Vol. 6, Issue 4 https://doi.org/10.1038/nchem.1899	journal	March 2014
Second-order spectral lineshapes from charged interfaces Ohno, Paul E.; Wang, Hong-fei; Geiger, Franz M. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01088-0	journal	October 2017
Surface-specific vibrational spectroscopy of the water/silica interface: screening and interference Schaefer, Jan; Gonella, Grazia; Bonn, Mischa Physical Chemistry Chemical Physics, Vol. 19, Issue 25 https://doi.org/10.1039/C7CP02251D	journal	January 2017
The structure of a lanthanide complex at an extractant/water interface studied using heterodyne-detected vibrational sum frequency generation Kusaka, Ryoji; Watanabe, Masayuki Physical Chemistry Chemical Physics, Vol. 20, Issue 4 https://doi.org/10.1039/C7CP06758E	journal	January 2018
Mechanism of phase transfer of uranyl ions: a vibrational sum frequency generation spectroscopy study on solvent extraction in nuclear reprocessing Kusaka, Ryoji; Watanabe, Masayuki Physical Chemistry Chemical Physics, Vol. 20, Issue 47 https://doi.org/10.1039/C8CP04558E	journal	January 2018
Surfactant-enhanced heterogeneity of the aqueous interface drives water extraction into organic solvents Servis, Michael J.; Clark, Aurora E. Physical Chemistry Chemical Physics, Vol. 21, Issue 6 https://doi.org/10.1039/C8CP06450D	journal	January 2019
Speciation of lanthanide ions in the organic phase after extraction from nitrate media by basic extractants Onghena, Bieke; Papagni, Eleonora; Souza, Ernesto Rezende RSC Advances, Vol. 8, Issue 56 https://doi.org/10.1039/C8RA06712K	journal	January 2018
Nanoscale view of assisted ion transport across the liquid–liquid interface Liang, Zhu; Bu, Wei; Schweighofer, Karl J. Proceedings of the National Academy of Sciences, Vol. 116, Issue 37 https://doi.org/10.1073/pnas.1701389115	journal	March 2018
Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS) Wang *, Hong-Fei; Gan † ‡, Wei; Lu † ‡ §, Rong International Reviews in Physical Chemistry, Vol. 24, Issue 2 https://doi.org/10.1080/01442350500225894	journal	April 2005
Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role? Knight, Andrew W.; Chiarizia, Renato; Soderholm, L. Solvent Extraction and Ion Exchange, Vol. 35, Issue 4 https://doi.org/10.1080/07366299.2017.1326770	journal	May 2017
Ions at the Air-Water Interface: An End to a Hundred-Year-Old Mystery? Levin, Yan; dos Santos, Alexandre P.; Diehl, Alexandre Physical Review Letters, Vol. 103, Issue 25 https://doi.org/10.1103/PhysRevLett.103.257802	journal	December 2009
Reverse Self-Assembly: (111)-Oriented Gold Crystallization at Alkylthiol Monolayer Templates Uysal, Ahmet; Stripe, Benjamin; Lin, Binhua Physical Review Letters, Vol. 107, Issue 11 https://doi.org/10.1103/PhysRevLett.107.115503	journal	September 2011
Unveiling Microscopic Structures of Charged Water Interfaces by Surface-Specific Vibrational Spectroscopy Wen, Yu-Chieh; Zha, Shuai; Liu, Xing Physical Review Letters, Vol. 116, Issue 1 https://doi.org/10.1103/PhysRevLett.116.016101	journal	January 2016
Electrostatic Origin of Element Selectivity during Rare Earth Adsorption Miller, Mitchell; Liang, Yihao; Li, Honghao Physical Review Letters, Vol. 122, Issue 5 https://doi.org/10.1103/PhysRevLett.122.058001	journal	February 2019
Structure and phase transitions in Langmuir monolayers Kaganer, Vladimir M.; Möhwald, Helmuth; Dutta, Pulak Reviews of Modern Physics, Vol. 71, Issue 3 https://doi.org/10.1103/RevModPhys.71.779	journal	April 1999
Stochastic fitting of specular X-ray reflectivity data using StochFit Danauskas, Stephen M.; Li, Dongxu; Meron, Mati Journal of Applied Crystallography, Vol. 41, Issue 6 https://doi.org/10.1107/S0021889808032445	journal	November 2008
Saturation of charge-induced water alignment at model membrane surfaces Dreier, Lisa B.; Nagata, Yuki; Lutz, Helmut Science Advances, Vol. 4, Issue 3 https://doi.org/10.1126/sciadv.aap7415	journal	March 2018

Similar Records

Ion-specific clustering of metal-amphiphile complexes in rare earth separations

Journal Article · 2020 · Nanoscale · OSTI ID:1783277

Nayak, Srikanth; Lovering, Kaitlin; Uysal, Ahmet

Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

Journal Article · 2017 · Solvent Extraction and Ion Exchange · OSTI ID:1389552

Knight, Andrew W.; Chiarizia, Renato; Soderholm, L.

Thiocyanate Ions Form Antiparallel Populations at the Concentrated Electrolyte/Charged Surfactant Interface

Journal Article · 2022 · Journal of Physical Chemistry Letters · OSTI ID:1905888

Kumal, Raju R.; Wimalasiri, Pubudu N.; Servis, Michael J.; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Interfaces
Ions
Lanthanides
Monolayers

Title: The Role of Specific Ion Effects in Ion Transport: The Case of Nitrate and Thiocyanate

Citation Formats

References (63)

Similar Records

Related Subjects